Azo dyes of the anthraquinone series



Patented Feb. 10, 1953 UNITED STATES i- ATENT OFFICE 2,628,230 Azo nYEsoFTHaj-A THRAQUINoNE SERIES Frederic B. -Stilmar, Wihnington, Del., assignorto E. I. du Pont de Nemours & Company, Wilmington, Del., a corporation of Delaware No Drawing. Application March 15, 1949,

. 1 Serial No. 81,617

and have the good iastness properties of dyesof this class in general. Several red dyes have been produced in the anthraquinone series, but they lack the strength or brightness or certain fastness properties, which are particularly desirable and which usuallyfidentify the; dyes of this class.

It is an object of: the present inventionto pro duce new vat dyes oi the anthraquinone series which dye in relatively bright; red shade ;v and which exhibit excellent fastnesspropertiesi and high tinctorial strength. A more specificiobj'ect of the invention is to produce oxdiazoles of the anthraquinone series by eiiecting' ring 1 closure of the acylated hydrazines produced by condensing l-aminoor 1-.nitroeanthraquinone-2- carbonyl hydrazines with organic dicarboxylic acid chlorides.

The acylated hydrazines employed as the starting intermediates for producing the dyes of the present invention are more particularly disclosed and claimed in my co-pending application Serial No. 81,616, filed'March 15, 1949. These acylated hydrazines, which have the general formula:

5? l i t t t.

are produced by reacting a l-aminoor i-nitroanthraquinone 2 carbonyl hydrazine with an organic dicarboxylic acid chloride of the formula: r

" s cla ms. (o1. ne -157) In the above formulae, R stands for a hydrocarbon radical of the group consisting of benzene and diphenyl radicals and X for a connecting bridge of the group consisting of N=N--, CH=CI-I-, Cllz, -O, S-, SO2- and CO ,,and Y stands for a substituent of the group consisting of -NH2 and --NO2. This class of acid chlorides is exemplified by azodiphenyl-dicarbonyl chlorides, stilbene-dicarbonyl chlorides, diphenylmethane-dicarbonyl chlorides, diphenylsulfide-dicarbonyl chlorides. diphenylether-dicarbonyl chlorides, diphenylsulfone-dicarbonyl chlorides and benzophenone-dicarbonyl chlorides.

According to the present invention, the acylated hydrazines produced from the dicarboxylic acid chlorides are subjected to a rin closure reaction which is brought about by the aid of acid condensing agents such as thionyl chloride, phosphorus oxychloride, p-toluene sulfonic acid, etc., in an inert solvent such as nitrobenzene or the chlorobenzenes. In this reaction the'hydrazide groups are ring closed to the oxdiazoles to give compounds of the general formula:

in which Y and R have the same significance as above given.

The following examples are given to illustrate the invention. The parts used are by Weight.

Example 1 8.5 parts of azobenzene-4A-dicarbonyl chloride, 20 parts of 1-nitroanthraquinone-2-carbonyl'hydrazine and 200 parts of nitrobenzene are mixed under agitation and slowly heated to -175 C. This temperature is maintained for one hour. The acylated hydrazine, in the form of light yellow needles, is filtered ofi, washed with benzene and dried.

Twenty (20) parts of this acylated hydrazine, 40 parts of thionyl chloride and 300 parts of nitrobenzene are heated under reflux at 165- C. for four hours. The resulting yellow nitroanthraquinone oxdiazole is filtered oii and 2,628,230 v j j v 3 4 washed with benzene and dried. It dissolves in sulfuric acid with a yellow color, and dyes cotton Example 3 from a red alkaline hydrosulfite vat in scarlet A mixture of 4.6 parts of azobipl1enyl--i,4-dishades of good fastness properties. It has the carbonyl chloride, 6.7 parts of l-aminoanthrafollowing formula: 5 quinone-2-carbcnyl hydrazine and 150 parts of The nitro groups are reduced to amino groups nitrobenzene is slowly heated to 170 C. and during the vatting. The nitro groups may also agitated for ten hours at this temperature. The

be replaced by amino groups by passing am.- acylated hydrazine, consisting of very fine orange monia through a suspension of the nitro oxdiparticles, is filtered oif and washed with benzene azole in nitrobenzene at 175 C. or by autoand dried. claving the nitro oxdiazole with*% NHdOH 2.3 parts of this acyla-ted hydrazine, 100 parts t 170 C, r of trichlorobenzene and 2 parts of p-toluene sul- The red colored aminoanthraquinone oxdi: fonic acid are heated to 200-210 C. for eight azole also dissolves in sulfuric acid with a yellow hours. The aminoantln'aquincne oxdiazole dyes color and dyes cotton fast. scarlet shades. cotton a scarlet-orange shade, redder and some- Example 2 what stronger than the unring closed starting I material, but it does not change color with alkali. A mixture of 9.2" parts of azobiphenyl-4A It has the formula: O NH:

It T 1 Cd? JO iw dicarbonyl chloride, 13.! parts of l-nitroanthraquinone-2-carbony1 hydrazine and 200 parts'of 3 3 nitrobenzene is slowly heated to 175-180 C. A mixture or" 5 parts of diphenylether-4,4'- and agitated for three hours at that tempera- 40 dicarboxylic acid, 150 parts of nitrobenzerie, 10 ture. The acylated hydrazine, which precipiparts of thionyl chloride and /100 part of pyridine tates as yellow plates, is filtered off, washed with is heated at 100-110 C. under reflux until solubenzene anddried. tion occurs (with the formation of the diacid Fifteen (15) parts of this acylated hydrazine, chloride). 30. parts of thionyl chloride and 250, parts of The excess thionyl chloride is removed by blownitrobenzene. are heated to 170%180" G. for four ing with av stream of air. and. there is then added hours. The brownish-yellownitroanthraquinone 13.2 parts of' 1-nitrcanthraquinohe-2ecarbonyl' oz diazole is filtered off and washed with benzene hydrazine.

and dried. It dyes cotton scarlet-orange shades After heating themass under agitation rat-160 from a red alkaline hydrosulfite vat. The dye- 165 0., for eight. hours, the acylated hydrazine ings are fast to alkali. It has the formula: isv filtered ofi; washed with benzene and dried.

O N 02 v n 1 n n v c o N=N The nitro groups are reduced to amino groups Six (6) parts of this acylated hydrazine, 13 in the vatting, but theymay also be replaced parts of thionyl chloride and 260- parts of orthoby amino groups with arnmonia in an inert sol- V dichlorobenzene are refluxed at 160-170 c; for vent'at- 1709-150 C. as described in Example 1. ten hours. The resulting nitroanthraquinone The 'aminoanthraquinone oxdiazole dissolves in oxdiazole, in the form of compact colorless cryssulfuric acid with a reddish-yellow color; and tals, is filtered oii, washed with benzene and dyes in scarlet-orange shades. 7 dried. It is represented by the formula:

5 6 The nitro groups are easilyreplaced by amino It is conveniently converted to thered crystal. groups when ammonia is passed through a nitroline aminoanthraquinone oxdiazole by passing benzene suspension at 175 C. The resulting ammonia through a nitrobenzene'solution of the amino oxdiazole is formed as bright red needles above colorless ox'dia zole, "asdescribed in the and dyes cotton in bright red shades from a red above examples. The resulting amino compound alkaline hydrosulfite vat. It dissolves in sulfuric has the formulaz- T r 7 acid with practically no color.

- I l N112 n u i ii 1| I c r V Example 5 Example 7 A mixture of 1.7 parts of diphenylsulf0ne-4,4'- 6.1 parts or azobenzene-3,3-dicarbonyl chlodicarbonyl chloride, 100 parts of ortho-dichlororide, 13.6 parts of 1-nitroanthraquinone-2-carbenzene and 3.4 parts of 1-nitroanthraquinone-2- bonyl hydrazine and 260 parts of ortho-dichlorocarbonyl hydrazine is heated slowly to 160-170 benzene are converted to the acylated hydrazine C. and held for two hours with stirring. The by heating to 160-170 C. for two hours. Then acylated hydrazine precipitates as small colorthere is added, under reflux, 23 parts of thionyl less crystals and is filtered oif, washed with benchloride.

zene and dried. Refluxing is continued for eight hours at 160 Three (3) parts of this acylated hydrazine, 7 170 C. The ring closed nitroanthraquinone oxparts of thionyl chloride and 130 parts of orthodiazole separates as microcrystalline needles.

dichlorobenzene are heated at l60-170 C. for These are filtered oif and washed with benzene, eight hours under reflux. The colorless chunky and dried. The light yellow product dissolves crystals of the nitroanthraquinone oxdiazole are in concentrated sulfuric acid with a yellow color.

filtered oif. It has the formula: It dyes cotton in fast red shades from the hyt. e t This nitroanthraquinone oxdiazole dissolves in drosulfite vat, during which process the nitro sulfuric acid with almost no color. groups are reduced to the corresponding amine. The above nitroanthraquinone oxdiazole may Before reduction of the nitro groups, it has the be converted to the aminoanthraquinone oxformula:

diazoledyestuff by passing ammonia through a 5 Diphenylmethane-3,3'-dicarbonyl chloride, dinitrobenzene suspension as described in the above phenylsulfide-4A'-dicarbonyl chloride or stilbeneexamples. The product separates as red needles 4,4'-dicarbonyl chloride may be substituted for which dye cotton in bluish-red shades. Its color the particular dicarbonyl chlorides employed in in sulfuric acid is an extremely weak yellow. the above examples to give new acylated anthra- Examn Z8 6 55 quinone-2-carbonyl hydrazines of similar reactivity and chemical properties. These com- One (1) part of benzophenone-4,4'-dicarbonyl pounds, when subjected to the action of the acid chloride, 2 parts of 1-nitroanthraquinone-2-carcondensing agents as illustrated in the above bonyl hydrazine and parts of ortho-dichloroexamples, are converted to bright red-to-scarlet benzene are mixed under agitation and the mix vat dyes having the good fastness properties of ture is heated at 160-170 C. for two hours. the anthraquinone vat dye class in general. Then, under reflux, there is added 4.5 parts of As illustrated in the above examples, the thionyl chloride. After eight hours heating at acylated hydrazines may be ring closed without 160-170 C., the colorless nitroanthraquinone oxisolation from the nitrobenzene or other solvent diazole of the following formula results: in which they are formed by adding the acid NN I n Q-a i u r o o It dyes cotton red shades from a bluish-red condensing agent and continuing the heating at colored vat. Its color in sulfuric acid is very pale the ring closure temperatures, generally within yellow, the range of from to 210 C.

The dyes of this invention are obtained in high yields andof relatively high purity. While ring closure to theokdiazole is preferably carried out at temperatures of from 160 to 170? C., this reaction may also be carried out at higher or lower temperatures such as from 130 C. to 210 C. The ring closure is preferably effected in an inert organic solvent such as the aromatic hydrocarbons or their nitrated or chlorinated derivatives, for instance, nitrobenzene, ortho-dichloroben'zene, trichlorobenzene and alpha-chloronaphthalene.

Where the dinitro-oxdiazole compound is obtained, it may be employed directly in the dyeing or printing process, for during the vatting step it is reduced to the corresponding amine. In most 15 the formula:

cases, however, the n-itro groups may be replaced by the amino groups through amination either with ammonia in an organic solvent at elevated temperatures or with ammonium hydroxide O NH2 i. The anthraquinone oxdiazole compounds of the general formula: l?

I Q. r 6 in which R stands for a hydrocarbon radical of the group consisting of benzene and diphenyl radicals and Y stands for a substituent of the group consisting of -NH2 and -NO2.

2. The anthraquinone oxdiazole compound of 8. The anthraquinone oxdiazole compound of the formula:

under pressure at temperatures of from 120? to 200 C. These new vat dyes may be purified,

when found desirable, by recrystallization from sulfuric acid or by treatment with oxidizing agent I? 5. The anthraquinone theformula:

oxdiazole compound of N N N u H H II II O\ 'N=N- C...

' o 6. The anthraquinone oxdiazole compound of the formula:

FREDERIC B. STILMAR.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES FATENTS,

Date

Number Name 2,175,803 I-Ionold et al Oct. 10, 1939 2,228,455 Honold et a1 Jan. 14, 1941 2,464,831 Stillmar Mar. 22, 1949 2,511,018 Stillmar June 13, 1950 

1. THE ANTHRAQUINONE OXDIAZOLE COMPOUNDS OF THE GENERAL FORMULA: 